title: Synthesis of 3-methoxyazetidines via an aziridine to azetidine rearrangement and theoretical rationalization of the reaction mechanism.
abstract: The synthetic utility of N-alkylidene-(2,3-dibromo-2-methylpropyl)amines and N-(2,3-dibromo-2-methylpropylidene)benzylamines was demonstrated by the unexpected synthesis of 3-methoxy-3-methylazetidines upon treatment with sodium borohydride in methanol under reflux through a rare aziridine to azetidine rearrangement. These findings stand in contrast to the known reactivity of the closely related N-alkylidene-(2,3-dibromopropyl)amines, which are easily converted into 2-(bromomethyl)aziridines under the same reaction conditions. A thorough insight into the reaction mechanism was provided by both experimental study and theoretical rationalization.
authors.affiliation: Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium.
authors.forename: Sonja
authors.initials: S
authors.lastname: Stanković
authors.forename: Saron
authors.initials: S
authors.lastname: Catak
authors.forename: Matthias
authors.initials: M
authors.lastname: D'hooghe
authors.forename: Hannelore
authors.initials: H
authors.lastname: Goossens
authors.forename: Kourosch
authors.initials: K
authors.lastname: Abbaspour Tehrani
authors.forename: Piet
authors.initials: P
authors.lastname: Bogaert
authors.forename: Michel
authors.initials: M
authors.lastname: Waroquier
authors.forename: Veronique
authors.initials: V
authors.lastname: Van Speybroeck
authors.forename: Norbert
authors.initials: N
authors.lastname: De Kimpe
mesh_terms: D001384:Azetidines / Q000138:chemical synthesis* / Q000737:chemistry; D001388:Aziridines / Q000138:chemical synthesis* / Q000737:chemistry; D001596:Benzylamines / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D008962:Models, Theoretical; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D001384:Azetidines; D001388:Aziridines; D001596:Benzylamines; C082735:azetidine; C033132:aziridine